Two bimetallic layered materials with "Cu4Fe3" defective cubane units:: syntheses, structures and magnetic properties of {[CuII(tn)]2[FeII(CN)6]}3•[Na3FeIII(CN)6]•12H2O (1) and {[CuII(tn)]2[FeII(CN)6]}•KCl•5H2O(2).

Reactions of the [Fe-III(CN)(6)](3-) anion with the [Cu-II(tn)](2+) ion (tn = 1,3-diaminopropane) afford the compounds {[Cu-II(tn)](2)[Fe-II(CN)(6)]}(3)center dot[Na3FeIII(CN)(6)]center dot 12H(2)O (1) and {[Cu-II(tn)](2)[Fe-II(CN)(6)]}center dot KCl.5H(2)O (2). Despite the differences concerning their asymmetric units, both structures present strong similar features: in both structures, the Cu(II) ion presents a square-base pyramidal CuN5 environment and each [Fe-II(CN)(6)](4-) anion is linked to six Cu(II) ions through its six N atoms leading to infinite [Cu-II(tn)](2)[Fe-II(CN)(6)] layers which can be viewed as 2-D layered arrangement generated by the defective cubane units Cu4Fe3 involving Fe-CN-Cu bridges. The most important differences between the two structures concern essentially the inter-layer arrangement which is occupied, in compound 1, by isolated paramagnetic [Fe(CN)(6)](3-) anions and water molecules, while in compound 2, this interlayer space is occupied by K+, Cl- ions and water molecules. Magnetic data indicate for 1 weak antiferromagnetic interactions and presence of magnetically isolated [Fe-III(CN)(6)](3-) anion and for 2 weak ferromagnetic interactions between the Cu(II) ions.